The poor stability of RuO_(2)electrocatalysts has been the primary obstacles for their practical application in polymer electrolyte membrane electrolyzers.To dramatically enhance the durability of RuO_(2)to construct ...The poor stability of RuO_(2)electrocatalysts has been the primary obstacles for their practical application in polymer electrolyte membrane electrolyzers.To dramatically enhance the durability of RuO_(2)to construct activity-stability trade-off model is full of significance but challenging.Herein,a single atom Zn stabilized RuO_(2)with enriched oxygen vacancies(SA Zn-RuO_(2))is developed as a promising alternative to iridium oxide for acidic oxygen evolution reaction(OER).Compared with commercial RuO_(2),the enhanced Ru–O bond strength of SA Zn-RuO_(2)by forming Zn-O-Ru local structure motif is favorable to stabilize surface Ru,while the electrons transferred from Zn single atoms to adjacent Ru atoms protects the Ru active sites from overoxidation.Simultaneously,the optimized surrounding electronic structure of Ru sites in SA ZnRuO_(2)decreases the adsorption energies of OER intermediates to reduce the reaction barrier.As a result,the representative SA Zn-RuO_(2)exhibits a low overpotential of 210 mV to achieve 10 mA cm^(-2)and a greatly enhanced durability than commercial RuO_(2).This work provides a promising dual-engineering strategy by coupling single atom doping and vacancy for the tradeoff of high activity and catalytic stability toward acidic OER.展开更多
The production of renewable fuels through water splitting via photocatalytic hydrogen production holds significant promise.Nonetheless,the sluggish kinetics of hydrogen evolution and the inadequate water adsorption on...The production of renewable fuels through water splitting via photocatalytic hydrogen production holds significant promise.Nonetheless,the sluggish kinetics of hydrogen evolution and the inadequate water adsorption on photocatalysts present notable challenges.In this study,we have devised a straightforward hydrothermal method to synthesize Bi_(2)O_(3)(BO)derived from metal‐organic frameworks(MOFs),loaded with flower-like ZnIn_(2)S_(4)(ZIS).This approach substantially enhances water adsorption and surface catalytic reactions,resulting in a remarkable enhancement of photocatalytic activity.By employing triethanolamine(TEOA)as a sacrificial agent,the hydrogen evolution rate achieved with 15%(mass fraction)ZIS loading on BO reached an impressive value of 1610μmol∙h^(−1)∙g^(−1),marking a 6.34-fold increase compared to that observed for bare BO.Furthermore,through density functional theory(DFT)and ab initio molecular dynamics(AIMD)calculations,we have identified the reactions occurring at the ZIS/BO S-scheme heterojunction interface,including the identification of active sites for water adsorption and catalytic reactions.This study provides valuable insights into the development of high-performance composite photocatalytic materials with tailored electronic properties and wettability.展开更多
By combination of the transient Raman spectroscopic measurement and the density functional theoretical calculations,the structural evolution and stability of TATB under shock compression was investigated.Due to the im...By combination of the transient Raman spectroscopic measurement and the density functional theoretical calculations,the structural evolution and stability of TATB under shock compression was investigated.Due to the improvement in synchronization control between two-stage light gas gun and the transient Raman spectra acquisition,as well as the sample preparation,the Raman peak of the N-O mode of TATB was firstly observed under shock pressure up to 13.6 GPa,noticeably higher than the upper limit of 8.5 GPa reported in available literatures.By taking into account of the continuous shift of the main peak and other observed Raman peaks,we did not distinguish any structural transition or any new species.Moreover,both the present Raman spectra and the time-resolved radiation of TATB during shock loading showed that TATB exhibits higher chemical stability than previous declaration.To reveal the detailed structural response and evolution of TATB under compression,the density functional theoretical calculations were conducted,and it was found that the pressure make N-O bond lengths shorter,nitro bond angles larger,and intermolecular and intra-molecular hydrogen bond interactions enhanced.The observed red shift of Raman peak was ascribed to the abnormal enhancement of H-bound effect on the scissor vibration mode of the nitro group.展开更多
With drilling and seismic data of Transtensional(strike-slip)Fault System in the Ziyang area of the central Sichuan Basin,SW China plane-section integrated structural interpretation,3-D fault framework model building,...With drilling and seismic data of Transtensional(strike-slip)Fault System in the Ziyang area of the central Sichuan Basin,SW China plane-section integrated structural interpretation,3-D fault framework model building,fault throw analyzing,and balanced profile restoration,it is pointed out that the transtensional fault system in the Ziyang 3-D seismic survey consists of the northeast-trending F_(I)19 and F_(I)20 fault zones dominated by extensional deformation,as well as 3 sets of northwest-trending en echelon normal faults experienced dextral shear deformation.Among them,the F_(I)19 and F_(I)20 fault zones cut through the Neoproterozoic to Lower Triassic Jialingjiang Formation,presenting a 3-D structure of an“S”-shaped ribbon.And before Permian and during the Early Triassic,the F_(I)19 and F_(I)20 fault zones underwent at least two periods of structural superimposition.Besides,the 3 sets of northwest-trending en echelon normal faults are composed of small normal faults arranged in pairs,with opposite dip directions and partially left-stepped arrangement.And before Permian,they had formed almost,restricting the eastward growth and propagation of the F_(I)19 fault zone.The F_(I)19 and F_(I)20 fault zones communicate multiple sets of source rocks and reservoirs from deep to shallow,and the timing of fault activity matches well with oil and gas generation peaks.If there were favorable Cambrian-Triassic sedimentary facies and reservoirs developing on the local anticlinal belts of both sides of the F_(I)19 and F_(I)20 fault zones,the major reservoirs in this area are expected to achieve breakthroughs in oil and gas exploration.展开更多
To satisfy the rapid development of gas-involving electrocatalysis(O2, CO2, N2, etc.), nanostructured electrocatalysts with favorably regulated electronic structure and surface nanostructures are urgently required. He...To satisfy the rapid development of gas-involving electrocatalysis(O2, CO2, N2, etc.), nanostructured electrocatalysts with favorably regulated electronic structure and surface nanostructures are urgently required. Herein, we highlighted a core-branch hydroxysulfide as a significantly enhanced oxygen evolution reaction electrocatalyst. This hydroxysulfide was facilely fabricated via a versatile interfacial reaction in S2- inorganic solution at room temperature for a designed period. The moderative growth kinetics contributed to the growth of interconnected hydroxysulfide nanosheets with high-sulfur contents on the hydroxide precursor substrates, resulting in a hierarchical nanostructure with multifunctional modifications, including regulated electronic structure, rapid electron highway, excellent accessibility, and facilitated mass transfer. Such synthetic methodology can be generalized and facilely governed by regulating the temperature, concentration, duration, and solvent for targeted nanostructures. Contributed to the favorably regulated electronic structure and surface nanostructure, the as-obtained core-branch Co2NiS2.4(OH)1.2 sample exhibits superior OER performance, with a remarkably low overpotential(279 m V required for 10.0 m A c^m-2), a low Tafel slope(52 m V dec^-1), and a favorable long-term stability. This work not only presents a promising nanostructured hydroxysulfide for excellent OER electrocatalysis, but also shed fresh lights on the further rational development of efficient electrocatalysts.展开更多
The presence of oxygen functional groups is detrimental to the capacitive performance of porous carbon electrode in organic electrolyte. In this regards, hydrogen thermal reduction has been demonstrated effective appr...The presence of oxygen functional groups is detrimental to the capacitive performance of porous carbon electrode in organic electrolyte. In this regards, hydrogen thermal reduction has been demonstrated effective approach in removing the unstable surface oxygen while maintaining the high porosity of carbon matrix. However, the exact evolution mechanism of various oxygen species during this process, as well as the correlation with electrochemical properties, is still under development. Herein, biomass-based porous carbon is adopted as the model material to trace its structure evolution of oxygen removal under hydrogen thermal reduction process with the temperature range of 400–800 °C. The optimum microstructure with low oxygen content of 0.90% and proper pore size distribution was achieved at 700°C. XPS, TPRMS and Boehm titration results indicate that the oxygen elimination undergoes three distinctive stages(intermolecular dehydration, hydrogenation and decomposition reactions). The optimum microstructure with low oxygen content of 0.90% and proper pore size distribution was achieved at 700 °C. Benefiting from the stable electrochemical interface and the optimized porous structure, the as-obtained HAC-700 exhibit significantly suppressed self-discharge and leak current, with improved cycling stability, which is attributable to the stabilization of electrochemical interface between carbon surface and electrolyte. The result provides insights for rational design of surface chemistry for high-performance carbon electrode towards advanced energy storage.展开更多
Developing a facile approach based on transition metal-based Prussian blue(PB)and its analogues(PBAs)with core-shell nanostructure is a very promising choice for constructing cost-effective electrocatalysts for oxygen...Developing a facile approach based on transition metal-based Prussian blue(PB)and its analogues(PBAs)with core-shell nanostructure is a very promising choice for constructing cost-effective electrocatalysts for oxygen evolution reaction(OER).Herein,a bimetallic core-shell structure with open cages of Fe-doped CoP(Fe-CoP cage)has been synthesized using CoFe-PBA cage-4 as precursor through a facile hydrothermal method and following phosphating process.Interestingly,there is an open hole in each face center of Fe-CoP cage,which suggests the more exposure of active sites for OER.Electrochemical measurements show that Fe-CoP cage can afford a current density of 10 mA cm-2 at a low overpotential(300 mV),which is better than that of RuO2.The excellent performance can be attributed to Fe doping composition and unique open-cage core-shell structure.The synergistic effect derived from bimetallic active for OER has been discussed.And its great catalytic stability has been evaluated via 1000 cycles of CV and chronoamperometry measurement.This work provides a potential method to design multiple transitional metal-doping electrocatalysts with complex framework derived from PBAs for water splitting.展开更多
Lithium ion batteries are important electrochemical energy storage devices for consumer electronics and the most promising candidates for electrical/hybrid vehicles. The surface chemistry influences the performance of...Lithium ion batteries are important electrochemical energy storage devices for consumer electronics and the most promising candidates for electrical/hybrid vehicles. The surface chemistry influences the performance of the batteries significantly. In this short review, the ewlution of the surface struture of the cathode materials at different states of the pristine, storage and electrochemical reaclions are summarized. The main methods for the surface modification are also introduced.展开更多
Efficient and durable oxygen evolution reaction(OER)requires the electrocatalyst to bear abundant active sites,optimized electronic structure as well as robust component and mechanical stability.Herein,a bimetallic la...Efficient and durable oxygen evolution reaction(OER)requires the electrocatalyst to bear abundant active sites,optimized electronic structure as well as robust component and mechanical stability.Herein,a bimetallic lanthanum-nickel oxysulfide with rich oxygen vacancies based on the La_(2)O_(2)S prototype is fabricated as a binder-free precatalyst for alkaline OER.The combination of advanced in situ and ex situ characterizations with theoretical calculation uncovers the synergistic effect among La,Ni,O,and S species during OER,which assures the adsorption and stabilization of the oxyanion SO_(4)^(2-)onto the surface of the deeply reconstructed porous heterostructure composed of confining Ni OOH nanodomains by La(OH)_3 barrier.Such coupling,confinement,porosity and immobilization enable notable improvement in active site accessibility,phase stability,mass diffusion capability and the intrinsic Gibbs free energy of oxygen-containing intermediates.The optimized electrocatalyst delivers exceptional alkaline OER activity and durability,outperforming most of the Ni-based benchmark OER electrocatalysts.展开更多
Perovskite LaCoO_(3) is being increasingly explored as an effective low-cost electrocatalyst for the oxygen evolution reaction(OER).Sr doping in LaCoO_(3)(La1-xSrxCoO_(3))has been found to substantially increase its c...Perovskite LaCoO_(3) is being increasingly explored as an effective low-cost electrocatalyst for the oxygen evolution reaction(OER).Sr doping in LaCoO_(3)(La1-xSrxCoO_(3))has been found to substantially increase its catalytic activity.In this work,we report a detailed study on the evolution of the electronic structure of La1-xSrxCoO_(3) with 0≤x≤1 and its correlation with electrocatalytic activity for the OER.A combination of X-ray photoemission spectroscopy(XPS)and X-ray absorption spectroscopy(XAS)was used to unravel the electronic density of states(DOS)near the Fermi level(EF),which provide insights into the key electronic structure features for the enhanced OER catalytic activity.Detailed analysis on the Co L-edge XAS suggest that LaCoO_(3) has a low spin state with t_(2g)^(6) e_(g)^(0) configuration at room temperature.This implies that the high OER catalytic activity of LaCoO_(3) should not be rationalized by the occupancy of eg=1 descriptor.Substituting Sr^(2+) for La^(3+) in LaCoO_(3) induces Co4+oxidation states and effectively dopes hole states into the top of valence band.A semiconductor-to-metal transition is observed for x>0.2,due to the holeinduced electronic DOS at the EF and increased hybridization between Co 3 d and O 2 p.Such an electronic modulation enhances the surface adsorption of the*OH intermediate and reduces the energy barrier for interfacial charge transfer,thus improving the OER catalytic activity in La_(1-x)Sr_(x)CoO_(3).In addition,we found that the La_(1-x)Sr_(x)CoO_(3) surface undergoes amorphization after certain period of OER measurement,leading to a partial deactivation of the electrocatalyst.High Sr doping levels accelerated the amorphization process.展开更多
This study aimed to investigate the mechanism of nitrogen doping,migration,and conversion during ammonia torrefaction and also explore the evolution law of the chemical structure of cellulose.The results showed that t...This study aimed to investigate the mechanism of nitrogen doping,migration,and conversion during ammonia torrefaction and also explore the evolution law of the chemical structure of cellulose.The results showed that the ammonia torrefaction pretreatment could significantly optimize the distribution of nitrogen and oxygen elements in cellulose.The carbon skeleton first captured the active nitrogenous radicals to form-NHn-N,and pyridine-N and pyrrole-N originated from the conversion of-NHn-N.The existence of C=O played a major role in the immobilization of nitrogen.The nitrogen in bio-oil exists mainly in the form of five-and six-membered heterocycles.The correlation analysis showed that the main precursors for the formation of nitrogenous heterocyclic compounds were five-membered Oheterocyclic compounds.Finally,the product distribution characteristics in the torrefaction-pyrolysis systems were summarized,and the nitrogen doping and conversion mechanisms were proposed.This study expanded the boundaries of cellulose pretreatment and the production of high-value chemicals.展开更多
The Tongnan secondary negative structure in central Sichuan Basin has controls and influences on the structural framework and petroleum geological conditions in the Gaoshiti-Moxi area.To clarify the controls and influ...The Tongnan secondary negative structure in central Sichuan Basin has controls and influences on the structural framework and petroleum geological conditions in the Gaoshiti-Moxi area.To clarify the controls and influences,the deformation characteristics,structural attributes and evolution process of the Tongnan negative structure were investigated through a series of qualitative and quantitative methods such as balanced profile restoration,area-depth-strain(ADS)analysis,and structural geometric forward numerical simulation,after comprehensive structural interpretation of high-precision 3D seismic data.The results are obtained in three aspects.First,above and below the P/AnP(Permian/pre-Permian)unconformity,the Tongnan negative structure demonstrates vertical differential structural deformation.It experiences two stages of structural stacking and reworking:extensional depression(from the Sinian Dengying Formation to the Permian),and compressional syncline deformation(after the Jurassic).The multi-phase trishear deformation of the preexisting deep normal faults dominated the extensional depression.The primary depression episodes occurred in the periods from the end of Late Proterozoic to the deposition of the 1st–2nd members of the Dengying Formation,and from the deposition of Lower Cambrian Longwangmiao Formation–Middle–Upper Cambrian until the Ordovician.Second,the multi-stage evolution process of the Tongnan negative structure controlled the oil and gas migration and adjustment and present-day differential gas and water distribution between the Tongnan negative structure and the Gaoshiti and Moxi-Longnüsi structural highs.Third,the Ordovician,which is limitedly distributed in the Tongnan negative structure and is truncated by the P/AnP unconformity on the top,has basic geological conditions for the formation of weathering karst carbonate reservoirs.It is a new petroleum target deserving attention.展开更多
Pyrolysis experiments were conducted on lacustrine organic-rich shale from Cangdong Sag in Bohai Bay Basin,China,to investigate the impact of hydrocarbon generation on shale pore structure evolution.Thermal evolution ...Pyrolysis experiments were conducted on lacustrine organic-rich shale from Cangdong Sag in Bohai Bay Basin,China,to investigate the impact of hydrocarbon generation on shale pore structure evolution.Thermal evolution is found to control the transformation of organic matter,hydrocarbon products characteristics,and pore structure changes.Furthermore,pore volume and specific surface area increase with increasing maturity.In low-mature stage,the retained oil content begins to increase,pore volumes show slight changes,and primary pores are occluded by the generated crude oil of high molecular weight and density.In the oil-window stage,the retained oil content rapidly increases and reaches maximum,and pore volumes gradually increase with increasing thermal maturity.At high mature stage,the retained oil content begins to decrease,and the pore volume increases considerably owing to the expulsion of liquid hydrocarbon.In over mature stage,natural gas content significantly increases and kerogen transforms to asphalt.Numerous organic pores are formed and the pore size gradually increases,resulting from the connection of organic pores caused the increasing thermal stress.This study lays a foundation for understanding variation of hydrocarbon products during the thermal evolution of lacustrine shales and its relationship with the evolution of shale reservoirs.展开更多
We try to figure out how the structure evolution and strategy evolution commonly affect the emergence of fair behaviors in the ultimatum game under a complex network framework.By allowing the players to change their n...We try to figure out how the structure evolution and strategy evolution commonly affect the emergence of fair behaviors in the ultimatum game under a complex network framework.By allowing the players to change their neighbors in the network as well as their strategies,several experiments have been conducted.Results of the simulations show that the coevolution has substantial impacts on the resulting outcomes for the strategy adopted as well as the ultimate structure.With increasing structure updating rate,players offer more in the ultimatum game,but players will offer less with increasing strategy updating rate.In particular,the ratio of structure updating to strategy updating also affects the emergence of fairness substantially because the larger the ratio,the more the players offer.In addition,the mutation in strategies plays a promoting role in the emergence of fairness.Moreover,the initial random network is evolved into the structure with small-world effects.By comparison with the traditional models of static structures,we show that allowing the network structure and strategy to coevolve generally promotes the emergence of fairness.展开更多
A structure model of urban traffic system evolution is built based on the analysis of the factors influencing the system evolution and the hierarchy between the factors. Then the influencing degrees of the factors are...A structure model of urban traffic system evolution is built based on the analysis of the factors influencing the system evolution and the hierarchy between the factors. Then the influencing degrees of the factors are quantificationally analyzed by DEMATE （decision making trial and evaluation laboratory）. The analysis results indicate that the traffic mode structure which achieves the highest central degree is the dominant influencing factor of the urban traffic system evolution, and that economy development and the traffic policy are the second important factors that also affect the Waffle mode structures. Furthermore, physical geography is a basic restriction to the urban traffic system evolution.展开更多
The evolution of a magnetic domain structure induced by temperature and magnetic field is reported in silicon- doped yttrium iron garnet （YIG） films with perpendicular anisotropy. During a cooling-down procedure fro...The evolution of a magnetic domain structure induced by temperature and magnetic field is reported in silicon- doped yttrium iron garnet （YIG） films with perpendicular anisotropy. During a cooling-down procedure from 300K to 7K, a 20% change in the domain width is observed, with the long tails of the stripes being shortened and the twisting stripes being straightened. Under the influence of the stray field of a barium ferrite, the garnet presents an interesting domain structure, which shows an appearance of branching protrusions. The intrinsic mechanisms in these two processes are also discussed.展开更多
Designing multicomponent integration catalysts(MICs)has been a promising strategy for improving electrocatalytic hydrogen evolution reaction(HER)due to the highly active interfaces as well as electronic synergy.Nevert...Designing multicomponent integration catalysts(MICs)has been a promising strategy for improving electrocatalytic hydrogen evolution reaction(HER)due to the highly active interfaces as well as electronic synergy.Nevertheless,many fundamental questions such as their actual active species and the influence on long-term stability remain to be answered.Herein,we present the structural evolution from a pseudotri-component electrocatalyst of nitrogen-doped carbon supported nickel/vanadium nitride/vanadium oxide(Ni-VN-V_(2)O_(3)/NC)nanorods to the heterostructural nickel/vanadium nitride(Ni-VN/NC)nanosheets during chemical or electrochemical processes.The self-reconstructed Ni-VN/NC exhibits a robust stability under alkaline conditions,while maintaining initial efficient HER activity with a low overpotential of 76 mV at the current density of 10 mA cm^(-2).Theoretical calculations and quasi-in-situ spectroscopic technology unveil the redistribution of electrons on the synergistic active interface,which synchronously optimizes the affinities for hydrogen,hydroxide,and water molecules,thereby remarkably accelerating the HER kinetics by reducing the barrier of Volmer step.展开更多
Oxygen evolution reaction(OER)as the foremost stumbling block to generate cost-effective clean fuels has received extensive attention in recent years.But,it still maintains the challenge to manipulate the geometric an...Oxygen evolution reaction(OER)as the foremost stumbling block to generate cost-effective clean fuels has received extensive attention in recent years.But,it still maintains the challenge to manipulate the geometric and electronic structure during single reaction process under the same conditions.Herein,we report a simple self-template strategy to generate honeycomb-like Ni_(2)P/N,P-C hybrids with preferred electronic architecture.Experiments coupled with theoretical results revealed that the synthesized catalyst has two characteristics:firstly,the unique honeycomb-like morphology not only enables the fully utilization of catalytic active sites but also optimizes the mass/electron transportation pathway,which favor the diffusion of electrolyte to accessible active sites.Secondly,N,P-C substrate,on the one hand,largely contributes the electronic distribution near Fermi level(E_(F))thus boosting its electrical conductivity.On the other hand,the support effect result in the upshift of d-band center and electropositivity of Ni sites,which attenuates the energy barrier for the adsorption of OH~àand the formation of*OOH.In consequence,the optimized Ni_(2)P/N,P-C catalysts feature high electrocatalytic activity towards OER(a low overpotential of 252 m V to achieve10 m A cm^(-2))and 10 h long-term stability,the outstanding performance is comparable to most of transition metal catalysts.This work gives a innovative tactics for contriving original OER electrocatalysts,inspirng deeper understanding of fabricating catalysts by combining theoretical simulation and experiment design.展开更多
Two-dimensional(2D)metal organic frameworks(MOFs)are emerging as low-cost oxygen evolution reaction(OER)electrocatalysts,however,suffering aggregation and poor operation stability.Herein,ultrafine Fe_(3)O_(4) nanopart...Two-dimensional(2D)metal organic frameworks(MOFs)are emerging as low-cost oxygen evolution reaction(OER)electrocatalysts,however,suffering aggregation and poor operation stability.Herein,ultrafine Fe_(3)O_(4) nanoparticles(diameter:6±2 nm)are homogeneously immobilized on 2D Ni based MOFs(Ni-BDC,thickness:5±1 nm)to improve the OER stability.Electronic structure modulation for enhanced catalytic activity is studied via adjusting the amount of Fe_(3)O_(4) nanoparticles on Ni-BDC.The optimal Fe_(3)O_(4)/Ni-BDC achieves the best OER performance with an overpotential of 295 mV at 10 mA cm^(-2),a Tafel slope of 47.8 mV dec^(-1) and a considerable catalytic durability of more than 40 h(less than 5 h for Ni-BDC alone).DFT calculations confirm that the active sites for Fe_(3)O_(4)/Ni-BDC are mainly contributed by Fe species with a higher oxidation state,and the potential-determining step(PDS)is the formation of the adsorbed O*species,which are facilitated in the composite.展开更多
The integrability of a （2＋1）-dimensional super nonlinear evolution equation is analyzed in the framework of the fermionie covariant prolongation structure theory. We construct the prolongation structure of the mult...The integrability of a （2＋1）-dimensional super nonlinear evolution equation is analyzed in the framework of the fermionie covariant prolongation structure theory. We construct the prolongation structure of the multidimen- sional super integrable equation and investigate its Lax representation. Furthermore, the Backlund transformation is presented and we derive a solution to the super integrable equation.展开更多
基金supported by the Taishan Scholar Program of Shandong Province,China (tsqn202211162)the National Natural Science Foundation of China (22102079)the Natural Science Foundation of Shandong Province of China (ZR2021YQ10,ZR2022QB163)。
文摘The poor stability of RuO_(2)electrocatalysts has been the primary obstacles for their practical application in polymer electrolyte membrane electrolyzers.To dramatically enhance the durability of RuO_(2)to construct activity-stability trade-off model is full of significance but challenging.Herein,a single atom Zn stabilized RuO_(2)with enriched oxygen vacancies(SA Zn-RuO_(2))is developed as a promising alternative to iridium oxide for acidic oxygen evolution reaction(OER).Compared with commercial RuO_(2),the enhanced Ru–O bond strength of SA Zn-RuO_(2)by forming Zn-O-Ru local structure motif is favorable to stabilize surface Ru,while the electrons transferred from Zn single atoms to adjacent Ru atoms protects the Ru active sites from overoxidation.Simultaneously,the optimized surrounding electronic structure of Ru sites in SA ZnRuO_(2)decreases the adsorption energies of OER intermediates to reduce the reaction barrier.As a result,the representative SA Zn-RuO_(2)exhibits a low overpotential of 210 mV to achieve 10 mA cm^(-2)and a greatly enhanced durability than commercial RuO_(2).This work provides a promising dual-engineering strategy by coupling single atom doping and vacancy for the tradeoff of high activity and catalytic stability toward acidic OER.
文摘The production of renewable fuels through water splitting via photocatalytic hydrogen production holds significant promise.Nonetheless,the sluggish kinetics of hydrogen evolution and the inadequate water adsorption on photocatalysts present notable challenges.In this study,we have devised a straightforward hydrothermal method to synthesize Bi_(2)O_(3)(BO)derived from metal‐organic frameworks(MOFs),loaded with flower-like ZnIn_(2)S_(4)(ZIS).This approach substantially enhances water adsorption and surface catalytic reactions,resulting in a remarkable enhancement of photocatalytic activity.By employing triethanolamine(TEOA)as a sacrificial agent,the hydrogen evolution rate achieved with 15%(mass fraction)ZIS loading on BO reached an impressive value of 1610μmol∙h^(−1)∙g^(−1),marking a 6.34-fold increase compared to that observed for bare BO.Furthermore,through density functional theory(DFT)and ab initio molecular dynamics(AIMD)calculations,we have identified the reactions occurring at the ZIS/BO S-scheme heterojunction interface,including the identification of active sites for water adsorption and catalytic reactions.This study provides valuable insights into the development of high-performance composite photocatalytic materials with tailored electronic properties and wettability.
基金supported by the National Natural Science Foundation of China(Grant Nos.12072299,11902276)the Natural Science Foundation of Sichuan Province(Grant No.2022NSFSC1802)+1 种基金the Basic Research Project of Southwest Jiaotong University(Grant No.2682023ZTPY009)the National Key Laboratory for Shock Wave and Detonation Physics of China(Grant No.JCKYS2019212007)。
文摘By combination of the transient Raman spectroscopic measurement and the density functional theoretical calculations,the structural evolution and stability of TATB under shock compression was investigated.Due to the improvement in synchronization control between two-stage light gas gun and the transient Raman spectra acquisition,as well as the sample preparation,the Raman peak of the N-O mode of TATB was firstly observed under shock pressure up to 13.6 GPa,noticeably higher than the upper limit of 8.5 GPa reported in available literatures.By taking into account of the continuous shift of the main peak and other observed Raman peaks,we did not distinguish any structural transition or any new species.Moreover,both the present Raman spectra and the time-resolved radiation of TATB during shock loading showed that TATB exhibits higher chemical stability than previous declaration.To reveal the detailed structural response and evolution of TATB under compression,the density functional theoretical calculations were conducted,and it was found that the pressure make N-O bond lengths shorter,nitro bond angles larger,and intermolecular and intra-molecular hydrogen bond interactions enhanced.The observed red shift of Raman peak was ascribed to the abnormal enhancement of H-bound effect on the scissor vibration mode of the nitro group.
基金Supported by the Key Project of National Natural Science Foundation of China(42330810).
文摘With drilling and seismic data of Transtensional(strike-slip)Fault System in the Ziyang area of the central Sichuan Basin,SW China plane-section integrated structural interpretation,3-D fault framework model building,fault throw analyzing,and balanced profile restoration,it is pointed out that the transtensional fault system in the Ziyang 3-D seismic survey consists of the northeast-trending F_(I)19 and F_(I)20 fault zones dominated by extensional deformation,as well as 3 sets of northwest-trending en echelon normal faults experienced dextral shear deformation.Among them,the F_(I)19 and F_(I)20 fault zones cut through the Neoproterozoic to Lower Triassic Jialingjiang Formation,presenting a 3-D structure of an“S”-shaped ribbon.And before Permian and during the Early Triassic,the F_(I)19 and F_(I)20 fault zones underwent at least two periods of structural superimposition.Besides,the 3 sets of northwest-trending en echelon normal faults are composed of small normal faults arranged in pairs,with opposite dip directions and partially left-stepped arrangement.And before Permian,they had formed almost,restricting the eastward growth and propagation of the F_(I)19 fault zone.The F_(I)19 and F_(I)20 fault zones communicate multiple sets of source rocks and reservoirs from deep to shallow,and the timing of fault activity matches well with oil and gas generation peaks.If there were favorable Cambrian-Triassic sedimentary facies and reservoirs developing on the local anticlinal belts of both sides of the F_(I)19 and F_(I)20 fault zones,the major reservoirs in this area are expected to achieve breakthroughs in oil and gas exploration.
基金supported by the National Key Research and Development Program(2016YFA0202500 and 2016YFA0200101)the Natural Scientific Foundation of China(21825501)
文摘To satisfy the rapid development of gas-involving electrocatalysis(O2, CO2, N2, etc.), nanostructured electrocatalysts with favorably regulated electronic structure and surface nanostructures are urgently required. Herein, we highlighted a core-branch hydroxysulfide as a significantly enhanced oxygen evolution reaction electrocatalyst. This hydroxysulfide was facilely fabricated via a versatile interfacial reaction in S2- inorganic solution at room temperature for a designed period. The moderative growth kinetics contributed to the growth of interconnected hydroxysulfide nanosheets with high-sulfur contents on the hydroxide precursor substrates, resulting in a hierarchical nanostructure with multifunctional modifications, including regulated electronic structure, rapid electron highway, excellent accessibility, and facilitated mass transfer. Such synthetic methodology can be generalized and facilely governed by regulating the temperature, concentration, duration, and solvent for targeted nanostructures. Contributed to the favorably regulated electronic structure and surface nanostructure, the as-obtained core-branch Co2NiS2.4(OH)1.2 sample exhibits superior OER performance, with a remarkably low overpotential(279 m V required for 10.0 m A c^m-2), a low Tafel slope(52 m V dec^-1), and a favorable long-term stability. This work not only presents a promising nanostructured hydroxysulfide for excellent OER electrocatalysis, but also shed fresh lights on the further rational development of efficient electrocatalysts.
基金National Science Foundation for Excellent Young Scholars of China (21922815)Key Research and Development (R&D) Projects of Shanxi Province (201903D121007)+3 种基金Natural Science Foundations of Shanxi Province (201801D221156)DNL Cooperation Fund of CAS (DNL180308)Science and Technology Service Network Initiative of CAS (KFJ-STS-ZDTP-068)Youth Innovation Promotion Association of CAS。
文摘The presence of oxygen functional groups is detrimental to the capacitive performance of porous carbon electrode in organic electrolyte. In this regards, hydrogen thermal reduction has been demonstrated effective approach in removing the unstable surface oxygen while maintaining the high porosity of carbon matrix. However, the exact evolution mechanism of various oxygen species during this process, as well as the correlation with electrochemical properties, is still under development. Herein, biomass-based porous carbon is adopted as the model material to trace its structure evolution of oxygen removal under hydrogen thermal reduction process with the temperature range of 400–800 °C. The optimum microstructure with low oxygen content of 0.90% and proper pore size distribution was achieved at 700°C. XPS, TPRMS and Boehm titration results indicate that the oxygen elimination undergoes three distinctive stages(intermolecular dehydration, hydrogenation and decomposition reactions). The optimum microstructure with low oxygen content of 0.90% and proper pore size distribution was achieved at 700 °C. Benefiting from the stable electrochemical interface and the optimized porous structure, the as-obtained HAC-700 exhibit significantly suppressed self-discharge and leak current, with improved cycling stability, which is attributable to the stabilization of electrochemical interface between carbon surface and electrolyte. The result provides insights for rational design of surface chemistry for high-performance carbon electrode towards advanced energy storage.
基金financially supported by Shandong Provincial Natural Science Foundation(ZR2017MB059)the Fundamental Research Funds for the Central Universities(18CX05016A)Postgraduate Innovation Project of China University of Petroleum(YCX2019096)。
文摘Developing a facile approach based on transition metal-based Prussian blue(PB)and its analogues(PBAs)with core-shell nanostructure is a very promising choice for constructing cost-effective electrocatalysts for oxygen evolution reaction(OER).Herein,a bimetallic core-shell structure with open cages of Fe-doped CoP(Fe-CoP cage)has been synthesized using CoFe-PBA cage-4 as precursor through a facile hydrothermal method and following phosphating process.Interestingly,there is an open hole in each face center of Fe-CoP cage,which suggests the more exposure of active sites for OER.Electrochemical measurements show that Fe-CoP cage can afford a current density of 10 mA cm-2 at a low overpotential(300 mV),which is better than that of RuO2.The excellent performance can be attributed to Fe doping composition and unique open-cage core-shell structure.The synergistic effect derived from bimetallic active for OER has been discussed.And its great catalytic stability has been evaluated via 1000 cycles of CV and chronoamperometry measurement.This work provides a potential method to design multiple transitional metal-doping electrocatalysts with complex framework derived from PBAs for water splitting.
基金supported by the Strategic Priority Research Program of the Chinese Academy of Sciences(Grant No.XDB07030200)the National Basic Research Program of China(Grant Nos.2014CB921002 and 2012CB921702)
文摘Lithium ion batteries are important electrochemical energy storage devices for consumer electronics and the most promising candidates for electrical/hybrid vehicles. The surface chemistry influences the performance of the batteries significantly. In this short review, the ewlution of the surface struture of the cathode materials at different states of the pristine, storage and electrochemical reaclions are summarized. The main methods for the surface modification are also introduced.
基金supported by National MCF Energy R&D Program of China(2018YFE0306105)National Key R&D Program of China(2020YFA0406104,2020YFA0406101)+10 种基金Innovative Research Group Project of the National Natural Science Foundation of China(51821002)National Natural Science Foundation of China(52201269,51725204,21771132,51972216,52041202)Natural Science Foundation of Jiangsu Province(BK20210735)Natural Science Foundation of the Higher Education Institutions of Jiangsu Province(21KJB430043)Collaborative Innovation Center of Suzhou Nano Science&Technologythe 111 ProjectSuzhou Key Laboratory of Functional Nano&Soft MaterialsJiangsu Key Laboratory for Advanced Negative Carbon Technologiesthe funding from Alexander von Humboldt(AvH)FoundationGusu leading talent plan for scientific and technological innovation and entrepreneurship(ZXL2022487)support from the German Federal Ministry of Education and Research in the framework of the project Catlab(03EW0015A/B)。
文摘Efficient and durable oxygen evolution reaction(OER)requires the electrocatalyst to bear abundant active sites,optimized electronic structure as well as robust component and mechanical stability.Herein,a bimetallic lanthanum-nickel oxysulfide with rich oxygen vacancies based on the La_(2)O_(2)S prototype is fabricated as a binder-free precatalyst for alkaline OER.The combination of advanced in situ and ex situ characterizations with theoretical calculation uncovers the synergistic effect among La,Ni,O,and S species during OER,which assures the adsorption and stabilization of the oxyanion SO_(4)^(2-)onto the surface of the deeply reconstructed porous heterostructure composed of confining Ni OOH nanodomains by La(OH)_3 barrier.Such coupling,confinement,porosity and immobilization enable notable improvement in active site accessibility,phase stability,mass diffusion capability and the intrinsic Gibbs free energy of oxygen-containing intermediates.The optimized electrocatalyst delivers exceptional alkaline OER activity and durability,outperforming most of the Ni-based benchmark OER electrocatalysts.
基金funding support by the National Natural Science Foundation of China (Grant No. 21872116)financial support by the National Natural Science Foundation of China (Grant No. 21621091 and 21373166)+5 种基金funding supported by the EU (ERC CoG HyMAP 648319)Spanish AEI (NyMPhA PID2019-106315RB-I00)“Comunidad de Madrid” and European Structural Funds for their financial support to FotoArt-CM project (S2018/NMT-4367)the Fundación Ramón Arecesfinancial support by the China Scholarship Council (CSC)the Sino-German Mobility Program (Grant No. M-0377)。
文摘Perovskite LaCoO_(3) is being increasingly explored as an effective low-cost electrocatalyst for the oxygen evolution reaction(OER).Sr doping in LaCoO_(3)(La1-xSrxCoO_(3))has been found to substantially increase its catalytic activity.In this work,we report a detailed study on the evolution of the electronic structure of La1-xSrxCoO_(3) with 0≤x≤1 and its correlation with electrocatalytic activity for the OER.A combination of X-ray photoemission spectroscopy(XPS)and X-ray absorption spectroscopy(XAS)was used to unravel the electronic density of states(DOS)near the Fermi level(EF),which provide insights into the key electronic structure features for the enhanced OER catalytic activity.Detailed analysis on the Co L-edge XAS suggest that LaCoO_(3) has a low spin state with t_(2g)^(6) e_(g)^(0) configuration at room temperature.This implies that the high OER catalytic activity of LaCoO_(3) should not be rationalized by the occupancy of eg=1 descriptor.Substituting Sr^(2+) for La^(3+) in LaCoO_(3) induces Co4+oxidation states and effectively dopes hole states into the top of valence band.A semiconductor-to-metal transition is observed for x>0.2,due to the holeinduced electronic DOS at the EF and increased hybridization between Co 3 d and O 2 p.Such an electronic modulation enhances the surface adsorption of the*OH intermediate and reduces the energy barrier for interfacial charge transfer,thus improving the OER catalytic activity in La_(1-x)Sr_(x)CoO_(3).In addition,we found that the La_(1-x)Sr_(x)CoO_(3) surface undergoes amorphization after certain period of OER measurement,leading to a partial deactivation of the electrocatalyst.High Sr doping levels accelerated the amorphization process.
基金sponsored by the National Natural Science Foundation of China(52176193)the National Key Research and Development Program of China(2019YFD1100602)+1 种基金the Shandong Provincial Natural Science Foundation,China(ZR2020ME184)the SDUT & Zhangdian City Integration Development Project(2021JSCG0013)。
文摘This study aimed to investigate the mechanism of nitrogen doping,migration,and conversion during ammonia torrefaction and also explore the evolution law of the chemical structure of cellulose.The results showed that the ammonia torrefaction pretreatment could significantly optimize the distribution of nitrogen and oxygen elements in cellulose.The carbon skeleton first captured the active nitrogenous radicals to form-NHn-N,and pyridine-N and pyrrole-N originated from the conversion of-NHn-N.The existence of C=O played a major role in the immobilization of nitrogen.The nitrogen in bio-oil exists mainly in the form of five-and six-membered heterocycles.The correlation analysis showed that the main precursors for the formation of nitrogenous heterocyclic compounds were five-membered Oheterocyclic compounds.Finally,the product distribution characteristics in the torrefaction-pyrolysis systems were summarized,and the nitrogen doping and conversion mechanisms were proposed.This study expanded the boundaries of cellulose pretreatment and the production of high-value chemicals.
基金Supported by the National Natural Science Foundation of China(U19B6003-01).
文摘The Tongnan secondary negative structure in central Sichuan Basin has controls and influences on the structural framework and petroleum geological conditions in the Gaoshiti-Moxi area.To clarify the controls and influences,the deformation characteristics,structural attributes and evolution process of the Tongnan negative structure were investigated through a series of qualitative and quantitative methods such as balanced profile restoration,area-depth-strain(ADS)analysis,and structural geometric forward numerical simulation,after comprehensive structural interpretation of high-precision 3D seismic data.The results are obtained in three aspects.First,above and below the P/AnP(Permian/pre-Permian)unconformity,the Tongnan negative structure demonstrates vertical differential structural deformation.It experiences two stages of structural stacking and reworking:extensional depression(from the Sinian Dengying Formation to the Permian),and compressional syncline deformation(after the Jurassic).The multi-phase trishear deformation of the preexisting deep normal faults dominated the extensional depression.The primary depression episodes occurred in the periods from the end of Late Proterozoic to the deposition of the 1st–2nd members of the Dengying Formation,and from the deposition of Lower Cambrian Longwangmiao Formation–Middle–Upper Cambrian until the Ordovician.Second,the multi-stage evolution process of the Tongnan negative structure controlled the oil and gas migration and adjustment and present-day differential gas and water distribution between the Tongnan negative structure and the Gaoshiti and Moxi-Longnüsi structural highs.Third,the Ordovician,which is limitedly distributed in the Tongnan negative structure and is truncated by the P/AnP unconformity on the top,has basic geological conditions for the formation of weathering karst carbonate reservoirs.It is a new petroleum target deserving attention.
基金supported by the National Natural Science Foundation of China(Grant Nos.42072150,41372144)the State Science and Technology Major Project of China(Grant No.2017ZX05049001-008)
文摘Pyrolysis experiments were conducted on lacustrine organic-rich shale from Cangdong Sag in Bohai Bay Basin,China,to investigate the impact of hydrocarbon generation on shale pore structure evolution.Thermal evolution is found to control the transformation of organic matter,hydrocarbon products characteristics,and pore structure changes.Furthermore,pore volume and specific surface area increase with increasing maturity.In low-mature stage,the retained oil content begins to increase,pore volumes show slight changes,and primary pores are occluded by the generated crude oil of high molecular weight and density.In the oil-window stage,the retained oil content rapidly increases and reaches maximum,and pore volumes gradually increase with increasing thermal maturity.At high mature stage,the retained oil content begins to decrease,and the pore volume increases considerably owing to the expulsion of liquid hydrocarbon.In over mature stage,natural gas content significantly increases and kerogen transforms to asphalt.Numerous organic pores are formed and the pore size gradually increases,resulting from the connection of organic pores caused the increasing thermal stress.This study lays a foundation for understanding variation of hydrocarbon products during the thermal evolution of lacustrine shales and its relationship with the evolution of shale reservoirs.
基金by the National Nature Science Foundation of China under Grant No 61004015the Research Fund for the Doctor Program of Higher Education of China under Grant No 20090032120034the Program for Changjiang Scholars and Innovative Research Team in University(PCSIRT).
文摘We try to figure out how the structure evolution and strategy evolution commonly affect the emergence of fair behaviors in the ultimatum game under a complex network framework.By allowing the players to change their neighbors in the network as well as their strategies,several experiments have been conducted.Results of the simulations show that the coevolution has substantial impacts on the resulting outcomes for the strategy adopted as well as the ultimate structure.With increasing structure updating rate,players offer more in the ultimatum game,but players will offer less with increasing strategy updating rate.In particular,the ratio of structure updating to strategy updating also affects the emergence of fairness substantially because the larger the ratio,the more the players offer.In addition,the mutation in strategies plays a promoting role in the emergence of fairness.Moreover,the initial random network is evolved into the structure with small-world effects.By comparison with the traditional models of static structures,we show that allowing the network structure and strategy to coevolve generally promotes the emergence of fairness.
文摘A structure model of urban traffic system evolution is built based on the analysis of the factors influencing the system evolution and the hierarchy between the factors. Then the influencing degrees of the factors are quantificationally analyzed by DEMATE （decision making trial and evaluation laboratory）. The analysis results indicate that the traffic mode structure which achieves the highest central degree is the dominant influencing factor of the urban traffic system evolution, and that economy development and the traffic policy are the second important factors that also affect the Waffle mode structures. Furthermore, physical geography is a basic restriction to the urban traffic system evolution.
基金Supported by the National Basic Research Program of China under Grant No 2013CB922304the National Natural Science Foundation of China under Grant No 91321310
文摘The evolution of a magnetic domain structure induced by temperature and magnetic field is reported in silicon- doped yttrium iron garnet （YIG） films with perpendicular anisotropy. During a cooling-down procedure from 300K to 7K, a 20% change in the domain width is observed, with the long tails of the stripes being shortened and the twisting stripes being straightened. Under the influence of the stray field of a barium ferrite, the garnet presents an interesting domain structure, which shows an appearance of branching protrusions. The intrinsic mechanisms in these two processes are also discussed.
基金supported by the National Natural Science Foundation of China(21901089,21901088,22161021 and 91622105)the Jiangxi Provincial Department of Science and Technology(20192BBEL50017,20172BCB22008 and 20192ACB20013)+1 种基金the support of Jiangxi Province(jxsq2018106041)the‘‘Young Elite Scientists Sponsorship Program”by CAST。
文摘Designing multicomponent integration catalysts(MICs)has been a promising strategy for improving electrocatalytic hydrogen evolution reaction(HER)due to the highly active interfaces as well as electronic synergy.Nevertheless,many fundamental questions such as their actual active species and the influence on long-term stability remain to be answered.Herein,we present the structural evolution from a pseudotri-component electrocatalyst of nitrogen-doped carbon supported nickel/vanadium nitride/vanadium oxide(Ni-VN-V_(2)O_(3)/NC)nanorods to the heterostructural nickel/vanadium nitride(Ni-VN/NC)nanosheets during chemical or electrochemical processes.The self-reconstructed Ni-VN/NC exhibits a robust stability under alkaline conditions,while maintaining initial efficient HER activity with a low overpotential of 76 mV at the current density of 10 mA cm^(-2).Theoretical calculations and quasi-in-situ spectroscopic technology unveil the redistribution of electrons on the synergistic active interface,which synchronously optimizes the affinities for hydrogen,hydroxide,and water molecules,thereby remarkably accelerating the HER kinetics by reducing the barrier of Volmer step.
基金supported by the Major Science and Technology Program for Water Pollution Control and Treatment(2017ZX07402001)the Ministry of Science and Technology of China for their financial support and the associated project is the Key Program for International S&T Cooperation Projects(No.2018YFE0124600)。
文摘Oxygen evolution reaction(OER)as the foremost stumbling block to generate cost-effective clean fuels has received extensive attention in recent years.But,it still maintains the challenge to manipulate the geometric and electronic structure during single reaction process under the same conditions.Herein,we report a simple self-template strategy to generate honeycomb-like Ni_(2)P/N,P-C hybrids with preferred electronic architecture.Experiments coupled with theoretical results revealed that the synthesized catalyst has two characteristics:firstly,the unique honeycomb-like morphology not only enables the fully utilization of catalytic active sites but also optimizes the mass/electron transportation pathway,which favor the diffusion of electrolyte to accessible active sites.Secondly,N,P-C substrate,on the one hand,largely contributes the electronic distribution near Fermi level(E_(F))thus boosting its electrical conductivity.On the other hand,the support effect result in the upshift of d-band center and electropositivity of Ni sites,which attenuates the energy barrier for the adsorption of OH~àand the formation of*OOH.In consequence,the optimized Ni_(2)P/N,P-C catalysts feature high electrocatalytic activity towards OER(a low overpotential of 252 m V to achieve10 m A cm^(-2))and 10 h long-term stability,the outstanding performance is comparable to most of transition metal catalysts.This work gives a innovative tactics for contriving original OER electrocatalysts,inspirng deeper understanding of fabricating catalysts by combining theoretical simulation and experiment design.
基金support from the Chinese Scholarship Council(201706220080)for W.H.the Natural Science Foundation of Hunan Province(2019JJ50526)for C.P.+1 种基金The Danish Council for Independent Research for the YDUN project(DFF 4093-00297)to J.Z.Villum Experiment(grant No.35844)for X.X.
文摘Two-dimensional(2D)metal organic frameworks(MOFs)are emerging as low-cost oxygen evolution reaction(OER)electrocatalysts,however,suffering aggregation and poor operation stability.Herein,ultrafine Fe_(3)O_(4) nanoparticles(diameter:6±2 nm)are homogeneously immobilized on 2D Ni based MOFs(Ni-BDC,thickness:5±1 nm)to improve the OER stability.Electronic structure modulation for enhanced catalytic activity is studied via adjusting the amount of Fe_(3)O_(4) nanoparticles on Ni-BDC.The optimal Fe_(3)O_(4)/Ni-BDC achieves the best OER performance with an overpotential of 295 mV at 10 mA cm^(-2),a Tafel slope of 47.8 mV dec^(-1) and a considerable catalytic durability of more than 40 h(less than 5 h for Ni-BDC alone).DFT calculations confirm that the active sites for Fe_(3)O_(4)/Ni-BDC are mainly contributed by Fe species with a higher oxidation state,and the potential-determining step(PDS)is the formation of the adsorbed O*species,which are facilitated in the composite.
基金Supported by the National Natural Science Foundation of China under Grant Nos 11605096,11547101 and 11601247
文摘The integrability of a （2＋1）-dimensional super nonlinear evolution equation is analyzed in the framework of the fermionie covariant prolongation structure theory. We construct the prolongation structure of the multidimen- sional super integrable equation and investigate its Lax representation. Furthermore, the Backlund transformation is presented and we derive a solution to the super integrable equation.
